Production of catalytic septa



Patented-July; 1940 uui'rso STATES PRODUCTION or curacy-r10 SEPTA William I. Hale, manna, Mich. a I

No Drawing. Original Serial No. .1873.

application June 13, 1936, Divided and this application October I, 1936, Serial No. 104,553. Renewed November 13, 1939 8 Claims. (OI. 23-233) The present invention relates to the production of composite catalysts and more particularly to the production of a catalytic mass containing hydrative and dehydrogenative catalysts, and is a division of my prior application Serial No. 85,182, filed June 13, 1936.

In certain reactions, such for example as the production of organic acids from their correspending alcohols or aldehydes by alternate de- 10 hydrogenation and hydration, special composite catalysts are desirable. As explained in my prior applications Ser. Nos. 571,281 and 574,033, organic acids maybe produced from their corresponding alcohols or aldehydes by reacting the alcohol or 15 aldehyde, in the presence of water, in vapor phase, witha catalytic mass including a dehydrogenative catalyst and a specially selected hydrative catalyst. In these circumstances the dehydrogenative catalyst functions todehydrogenate the alcohol to o the corresponding aldehyde and the hydrative catalyst functions to hydrate the aldehyde to an aldehydrol; the dehydrogenative catalyst then functions to effect the dehydrogenation of the aldehydrol, under the conditions of operation, to

25 the corresponding acid. 7

The present invention relates to the types of composite catalysts described in the application.

referredto but deals particularly with the production of these by novel methods to produce 30 more efiective catalytic action.

As indicated in the applications referred to, the typical dehydrogenative catalysts which are employable are copper, silver, gold, zinc, cobalt,

nickel, palladium and the platinum metals. Sim- 35 ilarly, a relatively wide range of hydrative catalysts may be utilized in this type of process or any analogous process which involves the alternate or simultaneous action of dehydrogenative and hydrative catalysts.

The directive catalytic base employed in the process is a compound capable of uniting with the aldehydrol as it is produced. It is found that chiefly organic acid salts of those bases, which salts undergo appreciable hydrolysis at the'tem- 45 perature of the reaction, fulfill this requirement. The hydroxides of such.metals, except possibly magnesium, are characterized as amphoteric electrolytes.- Such metals are copper, beryllium, magnesium, zinc, aluminum, gallium, lanthanum 50 and the yttrium metals, zirconium, cerium and a the cerium metals, chromium, uranium, manganese, iron, cobalt and nickel. Additional strictly hydrative catalysts may be used in conjunction 55 with these directive hydrative catalysts, such for example as the oxides of tungsten, vanadium, thorium, titanium and molybdenum."

It has been found in operating processes such as those described in the copending application referred to that the particular physical condition and area or surface of reaction of the catalyst is particularly important and furthermore the heat conductivity of the catalytic mass is likewise of salient importance.

Furthermore, in view of the fact that this type of reaction involves the production of free hydrogen, the withdrawal of this from .the reaction zone is an important condition of the process.

I have now found that processes of the character described in my prior applications can be considerably improved by producing the catalyst in preferred physical form.

In one phase of the invention an intimate, highly conductive mixture of unsintered activated dehydrogenative catalyst and hydrative catalyst is produced by fusing a reducible salt of the metal which ultimately is to act as the dehydrogenative catalyst in contact and admixture with a fusible or infusible salt of ametal whose oxide is to function in the process as the directive catalyst.

In operating the type ofprocess herein referred to, it has been found that the catalytic mass is unsuited to continuous action of dehydrogenation and hydration if such mass is in sintered or intumescent form. A completelyrigid state is most effective for the purpose at hand. Thus a catalyst prepared from a molten mass offers the best surface. 0 Furthermore the action of copper or other dehydrogenative metal produced from the molten condition serves admirably for heat conductance as these metallic particles lie close together and thus aflord enhanced control of temperature.

It has been suggested heretofore to first reduce to the molten condition the catalyst which is to 40 be employed or to fuse a compound of the catalyst and then reduce this compound. Thus in British Patent 19,249 of 1910 it is pointed out that hydrov genative catalysts, such as iron, cobalt and nickel, when heated to the molten condition, lose sulphur, arsenic, phosphorus and other deleterious substances. It is also here pointed out that a small percentage of diflicultly reducible oxides act as the promoters for the hydrogenation. The metals mentioned may be melted as such or in the form of their nitrates and other compounds which readily decompose into the metal at the higher temperatures employed.

Again British Patent 2,306 of 1914 describes the preparation of iron, cobalt, nickel or copper catalysts as hydrogenators and dehydrogenators of carbon compounds by incorporating with them traces of promoters, such as oxides or oxygen salts of an earthy metal inclusive of phosphates, molybdates, tungstates or selenates of alkaline earths. Good mixtures are eifected by precipitation of hydroxides or carbonates from soluble salts of metals concerned or by fusion of mixtures of the nitrates of such metals.

In Berichte 42,2097 of 1909 and Berichte 43,3387 of 1910 Ipatiew points out that the activity of copper in metallic form 'as a reducing agentmay be increased and -made efiective at lower temperatures by the use of ironand other promoters, and that a mixed metallic nickel-alumina catalyst was effective in bringing out the hydrogenation and dehydrogenation of phenol into cyclohexane at temperatures more than lower than could be achieved'by' nickel alone, followed by treatment with aluminum oxide.

In British Patent 11,816 of 1886 the preparation of copper oxide as a catalyst by the action of oxygen on the molten metal is described.

Again in British'Patent 147,958 of 1919 a process is described in which air is blown through refined molten copper to produce a liquid cuprous oxide which is then cooled, producing a catalyst of unusual purity,

Again British Patent 166,249 of 1920 describesa method of producing an oxide catalyst by melting cupric oxide, such'cupric oxide became purifled and was utilized in the dehydrogenation of different products.

Again it has been found in the past, as described in the, U. S. patent to Bosch l,1 i8,570, that the catalytic'emciency of iron, for the hydrogenation of nitrogen (in the synthesis of ammonia) can be increased by bringing together a compound of iron, such as the oxide, in molten condition in the presence of various promoters and reducing 'the iron oxide to the metallic state in which the promoters are evenly distributed. It is there pointed out that operation at high temperature dvantageous, tending to diminish the efliciency of the catalyst; to avoid this difficulty the promoters were employed to reduce the operating temperature.

In the present state of the art it becomes necessary to secure a dehydrogenative catalyst of great purity, high density and of marked porosity, and at the same time to intimately associate it with the particular amphoteric electrolytes which function as directive catalysts.

It has now been found that copper and other hydrogenative and dehydrogenative metals may be promoted by the incorporation of a suitable catalyst therein. Thus silver and copper, which are eifective dehydrogenative metals, are, according to the present process, brought into close relationship with hydrative catalysts by first melting the copper or equivalent metal-and some salt of the catalyst required, which latter can ultimately be converted to its corresponding oxide. In producing the ultimate composite catalyst the dehydrogenative metal is reduced to the metallic state. Thus particularly effective catalysts can be produced by utilizing silver or copper, or a mixture of silver and copper, with an oxide hydrative catalyst, such as zinc oxide, magnesium oxide and the like.

In another phase of the invention it has been found effective to melt an alloy of the metals concerned and to allow these molten metals to drop through an atmosphere of hydrogen sulphide or oxygen. Thus an alloy of copper and zinc con- It is also to be noted, as pointed out by Hugh ,Taylor, that the efllciency of a dehydrogenative catalyst can markedly be improved by oxidation and reduction at successively lower temperatures. In the present instance it has been found that the copper, zinc oxide catalyst reoxidizedat 350 C. and reducedto 300 C., and then again reoxidized at 300 C. and reduced at 250 C., may be brought into excellent condition to function eifectively at reactions operating as low as 200 C.

When an alloy of copper and zinc is melted, as described above, and dropped into a vessel supplied with a current of hydrogen sulphide, the molten cuprous sulphide collects with an even distribution of the zinc sulphide throughout the mass. When this molten mass is cooled, broken up and reduced with hydrogen, copper and zinc I metals are produced; when these are oxidized in air or oxygen and again reduced by hydrogen, a product comprising copper metal and zinc oxide is obtained. This particular catalyst is characterized by a more porous condition than where molten copper oxide matte of copper.

It will be appreciated from the description hereinbefore given that other salts of copper and zinc may be used; particularly valuable among these are the acetatesof these metals. Thus a mixture of copper and zinc acetates may be melted under appropriate conditions so as to insure uniform distribution of the two components, and the cooled mass may be broken up and reduced with hydrogen. Thereafter the reduced mass is oxidized and again reduced to establish the copper, zinc oxidestructure described. -Another method which has been found effective is the distillation of say the copper metal rective catalyst, which is employed in the ultimate composite catalyst, does not need to be brought into the molten state during the preparation. The principal requirement is only that it be evenly distributed throughout the copper or other dehydrogenative metal fram work. Hence zinc oxidemay be added to molten copper alone and this affords a good catalytic mass for the purposes of the present invention when it is oxidized and further reduced by hydrogen. Howconstituted the original ever, as will be appreciated, increased porosity of the ultimate catalyst is naturally insured when the dehydrogenative metals, such as copper, silver and thelike, are present in the original mass in the form of oxide or other salt and are reduced back to metallic state before service.

The special physical condition of the ultimate catalyst, by reason of this porous form, not only increases the efficiency of the catalyst itself but 6 found to serve admirably for the to it the potentialityjoi serving as a permeable membrane. 80 eflicient is this strucelement con- .0 as a catalyst and as a diiiusion septum tor hydrogen. The entire reaction was thus speeded up by reason or the removal or this one component, i. e. hydrogen. in the equilibrium system.

It will likewise be noted that'the catalyst itself 6 can be cased in a cylinder or other relatively massive element and used as'such without disintegration or breaking up. In such a condition, as will be appreciated, it serves very effectively in thermal control.

In the past considerable difllculty has been en countered in eiforts to secure a synthetic septunror membrane capable of permitting the selective transpiration ofany component out of a mixture of vaporous or gaseous components; It

would appear at first blush that there should be no difliculty in separating the small molecules of hydrogen from the more complex molecules of benzene. It has been :lound, however, that this is a diflicult problem and not entirely prac- I tical. Warrick 8a Mack (J. Amer. Chem. Soc. 55, 1324 (1933)) report interesting observations on separating hydrogen from benzene through a sieve made by heating a very thin brass sheet in a vacuum at from 400 to 900 C. The vaporizing of the zinc metal leaves channels in the copper through which hydrogen could difiuse or transpire. However, dificulties were met in that the large benzene molecules tended to plug up the channels to prevent further transpiration oi the hydrogen. Reheating the membrane to higher temperatures temporarily permitted further passage of the hydrogen.

It has been found that the known property of palladium can be efficiently employed in the present process to assist in the transmission of hydrogen through the membrane. Although there is a striking reaction of hydrogen at the surface of palladium, the transmission of hydrogen through the metal is slow unless the temperature is well elevated. However, marked advantages have been reported when a septum of palladium silver or palladium gold alloy is employed. Thus an alloy comprising 40% silver in palladium has been found to absorb four times as much hydrogen as pure palladium itself, and this paradoxically in view of the fact that silver itself does not absorb hydrogen. It is also reported that the transpiration of hydrogen by palladium is marked at about 240 C.

In the course of experimentation on the present process a. palladium silver alloy Was employed as a septum in a vessel containing mixed vapors of the present process (i. e., water, ethyl alcohol, acetaldehyde, acetic acid and hydrogen). It was found, however, that the transpiration of the hydrogen was very slow at the temperatures at which the reaction was carried out. However, it was found that when this palladium silver septum had previously been heated to a high temperature the transpiration of the hydrogen was considerably increased. This indicated a possible slight distillation of silver from the palladium alloy and the installation of capillary channels through which hydrogen could pass.

In further work it was found that zinc alloyed partially reduced cylinder with palladium can be removed efiectively and at a relatively low temperature when the alloy is heated in thevacuum. Thus operations carried out at 400 to 900 C. sufiice for removal of the zinc from a membrane comprising a palladium zinc alloy.

the resulting septum was found capable of transmitting hydrogen at low temperatures. It was furthermore found that an effective copper septum may be prepared by heating a brass to an elevated temperature and in a vacuum. In this latter case, however, as was reported byWarrick 8; Mack, it was found that the larger molecules tended to clog up the channels and prevent further transpiration of the smaller hydrogen molecules. The palladium, however, is particularly free from this disadvantage and appears to possess an inherent attraction-Ior the hydrogen above all other gases and pulls it along in the direction or the vacuum applied.

It is to be noted that for the removal of a volatile metal from an alloy of copper, palladium and the like, it is iound advantageous to slowly heat the alloy for the reason that there is less disruptive action on the ultimate channels formed within the residual metal. Alloys of copper with zinc, cadmium or lead are readily deprived of the low melting point metal by continued heating at relatively low temperatures and alloys or amalgams of copper with mercury were deprived of the mercury at the lowest temperature of all, namely 357 C.

It is now found that if palladium is associated with copp r, such as to serve as a coating or partial lining of the capillary walls or interstices, then hydrogen passes rapidly along such pal-f ladium surface, and especially under the effect of a vacuum. One efiective method of achieving this, for example, comp'rises heating a cylinder of an alloy of copper, zinc' and a little palladium slowly to between 400 to 900 C. Under these conditions most of the zinc is volatilized. The

thus treated cylinder was then used to enclose the catalyst of the present process and a mixture of water and alcohol or aldehyde vapors passed through the cylinder and in contact with the catalystat temperatures of the order of 300 C. By application of a vacuum outside of the walls of the cylinder, considerable hydrogen was withdrawn from within the chamber. Another method of procedure comprises utilizing a very high zinc content brass tube and after heating at temperatures sufliciently high to volatilize off most of the zinc the cylinder was soaked in palladious nitrate or other salt of palladium. Alter suchsaturation the cylinder was heated to drive of! the decomposition products. It was found that the palladium thus formed on the surface of the interstices or channels serves effectively for removal of the hydrogen from the metallic reaction zone.

It will be appreciated that metals other than those mentioned may be used in conjunction with copper, or with silver, gold and other dehydrogenative metals, in forming the septum for the transpiration of hydrogen. Thus mixtures or When the heating was carried out in a vacuum,

alloys of copper with lower :boiling point metals may be employed. When these are heated under the proper conditions to insure the volatilization or partial volatilization of the low boiling point metal, interstitial spaces or channels are set up within the copper mass, permitting the transpirationoi the hydrogen. Thus alloys and mixtures 01' copper and lead, copper and zinc, copper and cadmium, copper and lithi and mercury and the like may be utilized.

According to another method of procedure a such for example as the oxide which may be a formed on the interior surface of the septum by oxidation of the traces of-zinc present in the original brass tube, serves very eflectively for retaining such interior surface of the tube clear and unplugged by the larger molecules of gases. This is effected by reason of the action of the oxide in making and remaking salts with the acetic or other acid during the process.

It is to be observed at this point that the catalysts provided for according to the present invention differ markedly from earlier suggestions. such for example as described in the Legg U. S. Patent 1,401,117. Such prior suggestions comprise the fusion of a mass of copper oxide and the subsequent cooling and breaking up of the oxide mass. This oxide as such or the copper oxide reduced to some degree by hydrogen was employed as a catalyst. The catalyst of the present process in the first place is a composite and double functioning catalyst effecting both hydration and dehydrogenation. Furthermore, according to the present process the ultimate dehydrogenative and hydrative components oi the final catalyst are intimately dispersed by reason of fusion of one or both of the starting materials from which the ultimate catalysts are formed.

The activity of the hydrative components of the composite catalyst may further be accentuated by subjecting the catalystto the action of actinic rays in the manner fully described in my copending application Serial No. 748,928, filed October 18, 1934. I

The utility of the several types of composite catalysts described herein is shown in the following examples:

Example IA A quantity of silver, admixed with approximately 15% of its weight of zinc oxide and about 1% of its weight of thorium oxide, was iused in an atmosphere of oxygen. After cooling the mass was broken up and grams placed within an ordinary combustion tube and heated to 300 C. A stream of hydrogen was then passed through the tube until the reduction of the silver oxide was complete. Into the tube was now passed the mixed vapors of 46 grams (1 :mol) of Example IB Example IA was repeated in all details except that copper was employed in place of silver. It was found on analysis of the condensate that Copper shoe-27a- 1 the yield was about identical with that of Example IA.

\ Example [-0 Example IA was again repeated in all details except that about one-half of the silver was m placed with copper. Here again the yield was substantially the same as in Example IA.

Example II-A A definite weight of copper containing approximately 15% of zinc (i. e. brass) was melted in an atmosphere of oxygen. The mass was then cooled and broken up. 100 grams of the broken mass was then placed in a combustion tube and reduced with hydrogen at 300 C. Oxygen was admitted to the tube at 270 C. and the thus oxidized mass reduced with hydrogen at a temperature of 225 C.

There was then passed over this catalyst a mixture of vapors of 46 grams (1 mol) of ethyl alcohol and 36 grams (2 mols) of water fora period of one hour while maintained at a tem- Example II-B Into a combustion tube containing the catalyst described in Example II--'A was introduced a thimble of high zinc brass which had been heated in a vacuum to drive oil most of the zinc. This thimble was closed at one end and was connected at the other end to a vacuum pump. During. the treatment considerable hydrogen and a, trace of water and aldehyde was removed through the thimble.

Into the combustion tube were passed the mixed vapors of 46 grams (1 mol) of ethyl alcohol and 54 grams (3 mols)' of water for a period of one hour and at a temperature of approximately 2'70 C. The condensed efliuent vapors upon analysis were found to contain 59.8 grams of acetic acid and no aldehyde, thus representing practically a quantitative conversion. During the. process traces of aldehyde and water were condensed from the eflluent hydrogen vapors issuing through the vacuum pump.

Example III A catalyst was prepared by heating to the boiling point a mixture of copper and about 15% of its weight of zinc. The distilled vapors were collected, cooled and broken up. 100 grams of the broken mass were placed in a combustion tube,

oxidized with a stream of oxygen and then reduced with hydrogen at 300 C. The mass was reoxidized and again reduced at 270 C.

Through the combustion tube was then passed a vaporous mixture of 46 grams (1 mol) of ethyl alcohol and 36 grams (2 mols) of water over a period of one-hour and at a temperature of approximately 270 C. The condensate showed on analysis 41.5 grams of acetic acid. and a few grams of acetaldehyde, representing 69.2% conversion of alcohol to acid. By repeating this experiment under withdrawal of hydrogen by means of a porous thimble, as heretofore describech'the yield was easily raised to 96%.

Example IV Cuprous-sulphide containing 15% of its weight 2,206,773 of zinc sulphide was heated to the melting point,.

cooled and broken up. 100 grams of the mass was then placed in a combustion tube and reduced with hydrogen at from 300 to 350 C. The reduced mass was then oxidized and again reduced with hydrogen at approximately 300 0.

Through the tube was passed the mixed vapors of 46 grams (1 mol) of ethyl alcohol and 54 grams (3 mols) of water for a period of one hour' and at a temperature-of approximately 280 C.

Upon analysis the condensate was found to contain 40.4 grams of acetic acid and a few grams of acetaldehyde,thus representing a conversion of 67.3%. By repeating this experiment under withdrawal of hydrogen by means of a porous thimble, as heretofore described, the yield was easily raised to 95% of the theoretical.

. Example V A catalyst as prepared in Example IV was placed in a combustion tube and there was passed through the tube the mixed vapors of 60 grams propionic aldehyde, thus representing a conversion of 73% of the alcohol. By repeating this experiment under withdrawal of hydrogen by means of a porous thimble, as heretofore described, the yield was easily raised to 98% of the theoretically possible propionic acid derivable from N-propyl alcohol.

It will be appreciated that in actual operations the aldehydic fraction may be recycled with increased yield of acid. L

It is to be observed that the process described herein is operable with a wide range of starting materials. Thus organic acids may be produced from their corresponding aldehydes by utilizing a relatively concentrated alcohol and reactin this with given quantitiesrof water. Again, if desired, the process may be effectively carried out by using, as a starting material, the distillate of weak aqueous alcohols, such as beer and the like,

produced bytypical fermentation methods.

While preferred embodiments of the invention have been described, it is to be understood that these are given for the purpose of illustrating the principles involved and not as restricting the invention to the particular metho ds or materials described.

I claim:

1. A method of producing catalytically active septa which are permeable to hydrogen which comprises heating a septum of an alloy, the higher melting component of which is catalytically active, under conditions regulated to drive oil the lower boiling metal component to establish channels or interstices in the residual metal, and then establishing a quantity of palladium on the surface of such channels.

2. A method of producing catalytically active septa which are permeable to hydrogen which comprises heating a septum of an alloy, the-higher melting point component of which is catalytically active, under conditions regulated to drive oif the lower boiling point components and to establish channels or interstices in the residual metal, and depositing a quantity of palladium on the surface of such channels or interstices.

3. A method of producing catalytically active hydrogen permeable septa. which comprises forming a septum of an alloy of palladium, a dehydrogenative catalyst metal and a relatively low boiling point metal, heating the septum under conditions controlled to volatilize the lower boiling point metal and to establish channels or interstices throughout the residual metal structure.

4. A method of producing catalytically active hydrogen permeable septa which comprises forming a septum of an alloy of copper, zinc and palladium; heating the septum under conditions controlled to volatilize and remove a substantial quantity of the zinc and to establish channels or interstices throughout the residual metal.

5. A method of producing catalytically active septa which are selectively permeable to hydrogen which comprises heating a septum of an alloy, the higher melting point component of which is catalytically active under conditions regulated to drive 011 the lower boiling point components and to establish channels or interstices in the residual metal, saturating the septum with a solution of a palladium salt and heat treating the septum to deposit palladium on the surfaces of such channels or interstices.

6. A method of producing metallic septa capable of selectively permitting the transpiration of hydrogen forming a reaction zone containing hydrogen, alcoholic and acidic vapors which comprises forming a thin-walled septum of a poly-" nary alloy containing palladium and zinc; heating the septum under conditions controlled to volatilize and remove a substantial quantity of the zinc and to establish channels or interstices throughout the residual metal.

7. A method of producing catalytically active, hydrogen permeable septa which comprises forminga septum of copper, palladium and a metal chosen from the group consisting of zinc, cadmium, lead, lithium ,and mercury; heating the septum under. conditions controlled to volatilize and remove a substantial quantity of the lower boiling point metal and to establish channels or interstices throughout the residual metal.

8. A catalytically active septum selectively permeable to hydrogen which comprises a member consisting of an alloy of copper and palladium and which is penetrated throughout with minute channels 'or interstices capable of permitting the selective passage of hydrogen therethrough.

,WIILIAMLHALE, 

